JP5563421B2 - Method for obtaining yellow gold alloy deposits by electroplating without using toxic metals - Google Patents

Method for obtaining yellow gold alloy deposits by electroplating without using toxic metals Download PDF

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JP5563421B2
JP5563421B2 JP2010232903A JP2010232903A JP5563421B2 JP 5563421 B2 JP5563421 B2 JP 5563421B2 JP 2010232903 A JP2010232903 A JP 2010232903A JP 2010232903 A JP2010232903 A JP 2010232903A JP 5563421 B2 JP5563421 B2 JP 5563421B2
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クリストファ・ヘンツィロース
ギド・プランカート
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ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins

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Description

本発明は、厚い金合金層形態の電解析出物およびその製造方法に関する。   The present invention relates to an electrolytic deposit in the form of a thick gold alloy layer and a method for producing the same.

装飾めっきの分野において、９カラット以上の品位を有し、延性があり、１０ミクロンの厚さを有し、高度の耐変色性を有する、黄色をした金の電解析出を製造する方法が知られている。これらの析出物は、金および銅に加えて０．１から３ｇ・ｌ-1のカドミウムを含むアルカリ性の電解浴における電気分解によって得られる。 In the field of decorative plating, there is a known method for producing a yellow gold electrodeposition having a grade of 9 carats or more, ductility, a thickness of 10 microns and a high degree of discoloration resistance. It has been. These deposits are obtained by electrolysis in an alkaline electrolytic bath containing 0.1 to 3 g · l −1 cadmium in addition to gold and copper.

しかし、これらの既知の方法で得られる析出物は、１から１０％の間のカドミウム含有率を有する。カドミウムは、厚い層、すなわち、１から８００ミクロンの間の層の析出を促進し、合金に含まれる銅の量を減少させながら、黄色をした合金をもたらす。しかし、カドミウムは、極めて有毒であり、いくつかの国において禁止されている。   However, the precipitates obtained by these known methods have a cadmium content of between 1 and 10%. Cadmium promotes the deposition of thick layers, ie between 1 and 800 microns, resulting in a yellowed alloy while reducing the amount of copper contained in the alloy. However, cadmium is extremely toxic and is banned in some countries.

銅および亜鉛を含む、カドミウムを含まない１８カラットの合金も知られている。しかし、これらの析出物は、過度にピンク色の色調（銅が過剰）を有する。最後に、これらの析出物は、耐食性が乏しく、このことは急速に変色することを意味している。   Also known is an 18 carat alloy free of cadmium containing copper and zinc. However, these deposits have an excessively pink hue (copper excess). Finally, these deposits have poor corrosion resistance, which means that they rapidly change color.

その主成分として亜鉛もカドミウムも有さない、厚い、黄色をした金合金層を析出させるための製造方法を提供することによって、前述の欠点の全てまたは一部を克服することが本発明の目的である。   It is an object of the present invention to overcome all or part of the aforementioned drawbacks by providing a manufacturing method for depositing a thick, yellowish gold alloy layer that does not have zinc or cadmium as its main component. It is.

したがって、本発明は、アルカリ性の金シアン化物、有機金属化合物の形態の金属金、湿潤剤、金属イオン封鎖剤および遊離シアン化物を含む浴に浸漬させた電極に、金合金を電気めっき析出させる方法に関し、特に、前記浴が、複合の銅およびカリウムシアン化物(double copper and potassium cyanide) の形態の銅、およびシアン化物形態の銀を含み、鏡のように輝く黄色の金合金を電極上に析出させることを特徴とする。   Accordingly, the present invention provides a method for electroplating a gold alloy on an electrode immersed in a bath containing alkaline gold cyanide, metal gold in the form of an organometallic compound, a wetting agent, a sequestering agent and free cyanide. In particular, the bath contains copper in the form of double copper and potassium cyanide and silver in the form of cyanide and deposits a mirror-like yellow gold alloy on the electrode. It is characterized by making it.

本発明の他の有利な特徴によれば、
−上記浴は、アルカリ性のシアン化金形態の１から１０ｇ・ｌ-1の金属金を含み、
−上記浴は、アルカリ性の複合シアン化物(double cyanide)形態の３０から８０ｇ・ｌ-1の金属銅を含み、
−上記浴は、錯体形態の１０ｍｇ・ｌ-1から１ｇ・ｌ-1の銀金属を含み、
−上記浴は、１５から３５ｇ・ｌ-1のシアン化物を含み、
−湿潤剤は、０．０５から１０ｍｌ・ｌ-1の間の濃度を有し、
−湿潤剤は、ポリオキシアルケン、エーテルホスフェート、ラウリルサルフェート、ジメチルドデシルアミン−Ｎ−オキシド、ジメチル（ドデシル）アンモニウムプロパンスルホネートのうちから選択され、
−上記浴は、０．０１から５ｍｌ・ｌ-1の間の濃度のアミンを含み、
−上記浴は、０．１ｍｇ・ｌ-1から２０ｍｇ・ｌ-1の間の濃度の減極剤を含み、
−上記浴は、リン酸塩、炭酸塩、クエン酸塩、硫酸塩、酒石酸塩、グルコン酸塩および／またはホスホン酸塩タイプの導電塩を含み、
−上記浴の温度は、５０から８０℃の間に保たれ、
−上記浴のｐＨは、８から１２の間に保たれ、
−当該方法は、０．０５から１．５Ａ・ｄｍ-2の間の電流密度を用いて実施され、
−上記浴は、９．０８％の金、９０．８５％の銅および０．０７％の銀の比率を守る。 According to another advantageous feature of the invention,
The bath contains 1 to 10 g · l −1 metallic gold in alkaline gold cyanide form;
The bath contains 30 to 80 g · l −1 metallic copper in the form of an alkaline double cyanide;
The bath contains 10 mg · l −1 to 1 g · l −1 silver metal in complex form;
The bath contains 15 to 35 g · l −1 cyanide,
The wetting agent has a concentration between 0.05 and 10 ml·l −1 ;
The wetting agent is selected from among polyoxyalkenes, ether phosphates, lauryl sulfate, dimethyl dodecyl amine-N-oxide, dimethyl (dodecyl) ammonium propane sulfonate;
The bath contains an amine in a concentration between 0.01 and 5 ml·l −1 ;
The bath comprises a depolarizer at a concentration between 0.1 mg · l −1 and 20 mg · l −1 ;
The bath comprises phosphate, carbonate, citrate, sulfate, tartrate, gluconate and / or phosphonate type conductive salts;
The temperature of the bath is kept between 50 and 80 ° C.,
The pH of the bath is kept between 8 and 12,
The method is carried out using a current density between 0.05 and 1.5 A · dm −2 ;
-The bath protects the ratio of 9.08% gold, 90.85% copper and 0.07% silver.

本発明は、請求項のいずれかに記載の方法から得られた金合金形態の電解析出物に関わり、厚さが１から８００ミクロンの間に構成され、銅を含み、そして、第３の主要化合物として銀を、７５％の金、２１％の銅および４％の銀の比率で含んでいて、輝く３Ｎ色が得られることを特徴とするものである。   The present invention relates to an electrolytic deposit in the form of a gold alloy obtained from the method according to any of the claims, comprising a thickness between 1 and 800 microns, comprising copper, and a third It contains silver as a main compound in a ratio of 75% gold, 21% copper and 4% silver, and is characterized in that a bright 3N color can be obtained.

本発明は、３Ｎ色を有する金合金の電解析出に関わり、驚くべきことに、Ａｕ−Ｃｕ−Ａｇを主要化合物として知られていない比率で含むものであり、３Ｎ色すなわち輝きを呈する黄色が得られる。   The present invention relates to the electrolytic deposition of gold alloys having a 3N color, and surprisingly includes Au—Cu—Ag in a proportion not known as a main compound, and the can get.

上記の実施形態の析出物には、毒性の金属またはメタロイドを含まない、特にカドミウムを含まない、３Ｎ黄色、２００ミクロンの厚さ、優れた輝きを有し、極めて高度の摩耗および変色に対する耐性を有する金合金が存在する。   The deposits of the above embodiments are free of toxic metals or metalloids, especially cadmium free, 3N yellow, 200 microns thick, excellent shine, and extremely resistant to abrasion and discoloration. There are gold alloys.

この析出物は、次のタイプの電気分解によって電解浴にて得られる。
−金：５．５ｇ・ｌ-1；
−銅：５５ｇ・ｌ-1；
−銀：４０ｍｇ・ｌ-1；
−ＫＣＮ：２６ｇ・ｌ-1；
−ｐＨ：１０．５；
−温度：６５℃；
−電流密度：０．３Ａ・ｄｍ-2；
−湿潤剤：０．０５ｍｌ・ｌ-1ＮＮ＿ジメチルドデシルＮ−オキシド；
−イミノ二酢酸：２０ｇ・ｌ-1；
−エチレンジアミン：０．５ｍｌ・ｌ-1；
−ガリウム、セレンまたはテルル：１０ｍｇ・ｌ-1 This deposit is obtained in an electrolytic bath by the following type of electrolysis.
-Gold: 5.5 g · l -1 ;
-Copper: 55 g · l -1 ;
-Silver: 40 mg · l -1 ;
-KCN: 26 g · l -1 ;
-PH: 10.5;
-Temperature: 65 ° C;
Current density: 0.3 A · dm −2 ;
-Wetting agent: 0.05 ml·l -1 NN_dimethyldodecyl N-oxide;
-Iminodiacetic acid: 20 g · l -1 ;
Ethylenediamine: 0.5 ml·l −1 ;
-Gallium, selenium or tellurium: 10 mg · l -1

好ましくは、電気分解後に、最適な品質の析出物を得るために、２００から４５０℃の間の温度における１から３０分間の熱処理を行う。   Preferably, after electrolysis, a heat treatment is carried out for 1 to 30 minutes at a temperature between 200 and 450 ° C. in order to obtain optimal quality precipitates.

これらの条件は、９８ｍｇ・Ａ・ｍｉｎ-1の陰極の収率をもたらし、上記実施形態の場合、１時間当たり約１０μｍの析出速度をもたらす。 These conditions result in a cathode yield of 98 mg · A · min −1 and , in the case of the above embodiment, a deposition rate of about 10 μm per hour.

したがって、驚くべきことに、本発明による浴は、３Ｎ色、１８カラット析出物に対応する、約７５％の金、２１％の銅および４％の銀の比率の析出物をもたらし、当該比率は、上記の色に関する通常の電解析出における比率（約７５％の金、１２．５％の銅および１２．５％の銀と言う比率になる傾向にある）とは非常に異なっている。   Thus, surprisingly, the bath according to the present invention yields a deposit with a ratio of about 75% gold, 21% copper and 4% silver, corresponding to a 3N color, 18 carat deposit, which ratio is , Very different from the ratio in normal electrolytic deposition for the above colors (which tends to be about 75% gold, 12.5% copper and 12.5% silver).

上記浴は光沢剤も含み得る。これは好ましくは、ブチンジオール誘導体、ピリジノ−プロパンスルホネートまたは前記二者の混合物、スズ塩、ロート油、メチルイミダゾール、チオカルバミドなどのジチオカルボン酸、チオバルビツール酸、イミダゾリジンチオンまたはチオリンゴ酸である。   The bath may also contain a brightener. This is preferably a butynediol derivative, pyridino-propane sulfonate or a mixture of the two, tin salts, funnel oil, dithiocarboxylic acids such as methylimidazole, thiocarbamide, thiobarbituric acid, imidazolidinethione or thiomalic acid.

これらの実施形態において、上記電解浴は、断熱被覆されたポリプロピレンまたはＰＶＣ浴保持器に収容される。上記浴は、石英、ＰＴＦＥ、磁器、または安定化ステンレス鋼の浸漬電熱器(thermo-plunger)を用いて加熱する。良好な陰極棒の動きおよび電解液の流れを保つ必要がある。陽極は、白金めっきチタン、ステンレス鋼、ルテニウム、イリジウムまたは後二者の合金からなる。   In these embodiments, the electrolytic bath is housed in a heat-insulated polypropylene or PVC bath cage. The bath is heated using a quartz-, PTFE-, porcelain, or stabilized stainless steel thermo-plunger. It is necessary to maintain good cathode rod movement and electrolyte flow. The anode is made of platinum-plated titanium, stainless steel, ruthenium, iridium or the latter two alloys.

当然、本発明は、示した実施形態に限定されることはなく、当業者には明らかである様々な変形および変更が可能である。特に、上記浴は、極微量の以下の金属：Ｚｒ、Ｓｅ、Ｔｅ、Ｓｂ、Ｓｎ、Ｇａ、Ａｓ、Ｓｒ、Ｂｅ、Ｂｉを含み得る。   Of course, the present invention is not limited to the embodiments shown, and various modifications and changes will be apparent to those skilled in the art. In particular, the bath may contain trace amounts of the following metals: Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi.

さらに、湿潤剤は、アルカリ性シアン化物媒体中でぬれることができる任意のタイプのものであってよい。
Further, the wetting agent may be of any type that can be wetted in the alkaline cyanide medium.

Claims (11)

アルカリ性シアン化物形態の金属金、複合アルカリ性シアン化物形態の金属銅、および、シアン化物形態の金属銀、湿潤剤、金属イオン封鎖剤および遊離シアン化物を含む浴に浸漬した電極に、金合金を電気めっき析出させる方法であって、前記浴が、鏡のように輝く黄色の金合金を前記電極上に析出させ、前記浴が、９．０８重量％の金、９０．８５重量％の銅および０．０７重量％の銀の比率に守られており、析出物が７５重量％の金、２１重量％の銅および４重量％の銀を含み、輝く３Ｎ色が得られる、ことを特徴とする金合金の電気めっき析出方法。 Gold alloy is electroplated on an electrode immersed in a bath containing metallic gold in alkaline cyanide form, metallic copper in composite alkaline cyanide form, and metallic silver in cyanide form, wetting agent, sequestering agent and free cyanide. A method of plating deposition, wherein the bath deposits a mirror-like yellow gold alloy on the electrode, the bath comprising 9.08 wt % gold, 90.85 wt % copper and 0 0.07% by weight silver, characterized in that the deposit contains 75% by weight gold, 21% by weight copper and 4% by weight silver, giving a brilliant 3N color Electroplating deposition method for alloys. 前記浴が、アルカリ性シアン化金形態の５．５ｇ・ｌ-1の金属金、５５ｇ・ｌ-1の複合アルカリ性シアン化物形態の金属銅および錯体形態の４０ｍｇ・ｌ-1の金属銀を含むことを特徴とする、請求項１に記載の方法。 The bath comprises 5.5 g · l −1 metallic gold in alkaline gold cyanide form, 55 g · l −1 metallic copper in complex alkaline cyanide form and 40 mg · l −1 metallic silver in complex form The method of claim 1, wherein: 前記浴が、１５から３５ｇ・ｌ-1の遊離シアン化物を含むことを特徴とする、請求項２に記載の方法。 The process according to claim 2, characterized in that the bath contains 15 to 35 g · l -1 free cyanide. 前記湿潤剤が、ポリオキシアルケン、エーテルホスフェート、ラウリルサルフェート、ジメチルドデシルアミン−Ｎ−オキシド、および、ジメチル（ドデシル）アンモニウムプロパンスルホネートからなる群から選択されることを特徴とする、請求項１から３のいずれかに記載の方法。   The humectant is selected from the group consisting of polyoxyalkenes, ether phosphates, lauryl sulfate, dimethyl dodecyl amine-N-oxide, and dimethyl (dodecyl) ammonium propane sulfonate. The method in any one of. 前記湿潤剤が、０．０５から１０ｍｌ・ｌ-1の間の濃度を含むことを特徴とする、請求項４に記載の方法。 5. A method according to claim 4, characterized in that the wetting agent comprises a concentration between 0.05 and 10 ml·l −1 . 前記浴が、０．０１から５ｍｌ・ｌ-1の間の濃度のアミンを含み、ここでアミンがエチレンジアミンであることを特徴とする、請求項１から５のいずれかに記載の方法。 6. A process according to any one of claims 1 to 5, characterized in that the bath comprises an amine concentration between 0.01 and 5 ml·l −1 , wherein the amine is ethylenediamine. 前記浴が、リン酸塩、炭酸塩、クエン酸塩、硫酸塩、酒石酸塩、グルコン酸塩および／またはホスホン酸塩を導電塩として含むことを特徴とする、請求項１から６のいずれかに記載の方法。   7. The bath according to claim 1, characterized in that the bath contains phosphate, carbonate, citrate, sulfate, tartrate, gluconate and / or phosphonate as conductive salts. The method described. 前記浴の温度が、５０から８０℃の間に維持されることを特徴とする、請求項１から７のいずれかに記載の方法。   The method according to any one of claims 1 to 7, characterized in that the temperature of the bath is maintained between 50 and 80 ° C. 前記浴のｐＨが、８から１２の間に維持されることを特徴とする、請求項１から８のいずれかに記載の方法。   9. A method according to any of claims 1 to 8, characterized in that the pH of the bath is maintained between 8 and 12. ０．３Ａ・ｄｍ-2の電流密度で実施されることを特徴とする、請求項１から９のいずれかに記載の方法。 The method according to claim 1, wherein the method is performed at a current density of 0.3 A · dm −2 . 請求項１から１０のいずれかに記載の方法から得られる金合金形態の電解析出物であって、厚さが１から８００ミクロンの間であり、銅を含み、そして、第３の主要化合物として銀を含み、輝く３Ｎ色が得られること、および、７５重量％の金、２１重量％の銅および４重量％の銀を含み、輝く３Ｎ色が得られることを特徴とする電解析出物。 Electrodeposit in the form of a gold alloy obtained from the method according to any of claims 1 to 10, having a thickness between 1 and 800 microns, comprising copper, and a third main compound Electrolytic deposits characterized in that a shining 3N color is obtained with silver as a light source and a shining 3N color with 75% by weight gold, 21% by weight copper and 4% by weight silver. .
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US20150027898A1 (en) 2015-01-29
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US9567684B2 (en) 2017-02-14
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EP2312021A1 (en) 2011-04-20
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